Dodecyl tertiaryaminoethyl sulfoxides



United States Patent 3,364,213 DODECYL TERTEARYAlt IINOETHYL SULFOXEESHill M. Priestley, North Bergen, and James H. Wiison, Demarest, Ni,assignors to Lever Brothers Company, New York, N.Y., a corporation ofMaine No Drawing. 'Continuation-in-part of application Ser. No. 365,437,May 6, 1964. This appiication May 1, 1967, Ser. No. 634,873

5 Claims. (Cl. 269-247 .1)

ABSTRACT OF THE DiSiILGSURE The novel sulfoxides, dodecylZ-dimethylamino-ethyl sulfoxide, dodecyl Z-diethanolaminoethylsulfoxide, dodecyl 2-morpholinoethyl sulfoxide and dodecyl2-piperidinoethyl sulfoxide, are disclosed. The sulfoxides havesuds-stabilizing activity and are germicides.

The present invention relates to novel dodecyl 2-aminoethyl sulfoxideswhich are useful as foam stabilizers and which have germicidalproperties.

This application is a continuation-in-part of our copending application,Ser. No. 365,487, filed May 6, 1964, which in turn was acontinuation-in-part of our applications, Ser. Nos. 725,505, filed Apr.1, 1958, and 60,546, filed Oct. 5, 1960, all now abandoned.

Alkyl sulfoxides having a lOng chain fatty acid residue are known tohave surface active properties. US. Patent No. 2,787,595 to Webbdiscloses the the use of alkyl sulfoxides as the essential activeingredient in detergent compositions. According to Webb, the sulfoxidesmay be employed per so as the essential active ingredient in detergentcompositions, but preferably are employed in combination with inorganicbuilder salts. It is also stated in the patent that other syntheticdetergents may be employed as detergency supplements in combination withthe sulfoxides and that foam stabilizers may be added.

It is common practice in the industry to include foam stabilizers indetergent compositions to improve the persistence and stability of thefoam produced by agitation of the washing solution containing thedetergent composition. These foam stabilizers are particularly useful indetergent compositions based upon organic non-soap synthetic detergentcompounds.

The present invention is concerned with compounds which stabilize thefoam produced on agitation of an aqueous washing solution containing asuds-producing organic synthetic detergent. Foam persistence isgenerally used by the housewife as an index of the cleansing ability ofthe solution. Once the foam has collapsed and disappeared, the housewifebelieves that the fat emulsifying and other cleansing abilities of thesolution have been used up. This is not necessarily true, however, asthe foam may collapse before the cleansing ability of the solution hasbeen consumed. The problem of stabilizing the foam of aqueous solutionsof detergent compositions is thus an important one and is one which hasreceived considerable attention by workers in the field.

In addition to stability, several other characteristics of the foam areinvolved. The original amount of foam produced on agitation of theaqueous solution is an important consideration. Furthermore, the textureof the foam,

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Le, whether it is open and coarse, or of a very fine, dense character,and the ability of the foam to rinse cleanly and quickly from thearticles being washed are factors which must be taken intoconsideration.

The prior art compounds which function as foam stabilizers in detergentsystems depend upon well known foam stabilizing functional linkages,such as amide, and alcoholic and phenolic hydroxyl groups. Examples ofthese materials include fatty alcohols such as lauric alcohol and fattyacid substituted amides such as lauric diethanol amide and lauricisopropanol amide. Parahydroxy laurophenone is an example of a foamstabilizing compound containing a phenolic hydroxyl group.

These prior art foam stabilizers have some degree of specificity, i.e.,they are suitable for use in stabilizing the foams produced in aqueoussolutions of certain sudsproducing organic detergent compounds. Forexample, parahydroxy laurophenone is effective only with sodium laurylsulfate or mixtures of this with other compatible active detergents.Also, the above-mentioned amides are generally suitable for use withalkyl aryl sulfonates, and lauryl alcohol is generaliy suitable for usewith alkyl aryl sulfonates, and lauryl alcohol is generally limited touse with alkyl sulfates.

Still another deficiency of prior art foam stabilizers is that whilethey are effective in experimental systems based on pure water, theireffectiveness is considerably diminished or non-existent in the presenceof soil or fatty materials.

In accordance with the present invention, novel compounds are providedhaving the following formula:

wherein R is an amino radical selected from the group consisting ofdimethylamino, diethanolamino, morpholino and piperidino radicals.

The compounds falling within this description are dodecylZ-dimethylaminoethyl sulfoxide,

C H SOCH CH N (CH 2 dodecyl Z-diethanolaminoethyl sulfoxide,

C H SOCH CH N(CH CH OH) dodecyl 2-morpholino-et-hyl sulfoxide,

C1zH25SOCH2CHzN /O CHE-CH3 and dodecyl 2-piperidinoethyl sulfoXide,

CHa-CHa CH1 GET-CH2 It has been found that the presence of small amountsof the sulfoxides described above improve the stability of the foamproduced by agitating aqueous solutions of sudsproducing materialsselected from the group consisting of anionic, ampholytic and nonionicorganic synthetic detergents. In addition, these compounds impartgermicidal characteristics to aqueous solutions containing them.

The term suds-producing materials selected from the group consisting ofanionic, ampholytic and nonionic organic synthetic detergents, asemployed herein, is intended to include those anionic, ampholytic andnonionic compounds which are commonly employed as the essential activeingredient of suds-producing detergent compositions.

Suitable anionic suds-producing organic synthetic detergents include thealkyl aryl sulfonates, such as sodium dodecyl benzene sulfonate orammonium pentadecyl benzene sulfonate, and the methyl taurates, such asIgepon TK-32, a sodium N-methyl-N- tall oil acid taurate, and IgeponTE42, an N-methyl acyl taurate derived from tallow. Also included arethe sulfated fatty alcohols, such as sodium lauryl sulfate and ammoniumlauryl alcohol sulfate; the sulfated polyethylene oxide esters of resinsor fatty acids, such as the ammonium salt of sulfated nonyl phenolcondensed with four moles of ethylene oxide; and Sipon LT-6, a.triethanolamine lauryl alcohol sulfate.

Suitable nonionic suds-producing organic synthetic detergents which maybe employed according to this invention include Oronite NI-8589, adodecyl phenol condensed with more than 10, i.e., 20 to 30 moles ofethylene oxide; Triton X-100, an alkyl aryl polyether alcohol, i.e.,octylphenol condensed with moles of ethylene oxide; and Tergitol NP-14,an alkyl phenol polyethylene glycol ether; Neutronyx 600, an aromaticpolyglycol ether condensate; and Sterox A], a tridecyl alcohol condensedwith 10 moles of ethylene oxide, and Sterox CD, a tall oil condensedwith 10 moles of ethylene oxide.

Also suitable are Deriphat No. 154, a tallow disodium betaiminodipropionate, and sodium cocoglycinate. These are ampholytic substances.

Conventional soaps and inorganic builder salts, such as the phosphates,silicates, sulfates and the like, are not included within the termsuds-producing materials selected from the group consisting of anionic,ampholytic and nonionic organic synthetic detergents used herein,although these materials can be used as auxiliary agents in thecompositions of this invention. Also excluded from this class are thesulfoxides described in the aforementioned Webb patent as an essentialactive ingredient in detergent compositions. The benefits of thisinvention are not obtained by merely increasing the concentration ofdialkyl sulfoxide in the detergent composition.

The level of sulfoxide required to provide optimum foam stabilitydepends upon the particular organic synthetic detergent employed andupon the nature of the sulfoxide. Generally speaking, the sulfoxides areefiective at levels above about 0.1% in detergent compositionscontaining operable levels of suds-producing organic syntheticdetergents. At levels below this range, little if any benefit isobtained.

A general type of reaction which may be employed in preparing sulfoxidesof this invention is described in detail in US. Patent No. 2,787,595.

The following example illustrates a method of preparing pure sulfoxidesin accordance with the present in- Vention.

Example 1 Dodecyl vinyl sulfoxide was prepared from dodecylZ-hydroxyethiyl sulfide. The preparation is summarized by the followingequations:

The intermediate chlorosulfinate C H SCH CH O SOCl is quite stable andwas heated at 200 C. under reduced pressure to drive out all of thesulfur dioxide, leaving the dodecyl Z-chloroethyl sulfide. The latter,by oxidation with sodium hypochlorite solution or concentrated nitricacid, gave dodecyl 2-chloroethyl sulfoxide. This was converted tododecyl 2-iodoethyl sulfoxide by action of sodium iodide in acetonesolution. Dodecyl vinyl sulfoxide, M.P. 42, was formed by heating2-iodoethyl sulfoxide with 10% aqueous sodium hydroxide for 2 hours at80 C. with mechanical stirring.

Amino sulfoxides may be prepared from these intermediates. For example,dodecyl Z-dimethylaminoethyl sulfoxide is prepared by mixing 8 grams ofdodecyl 2- chloroethyl sulfoxide, 16 ml. of a 45% dimethylamine solutionin methanol, and 32 ml. of methanol and keeping the mixture in amagnesium citrate bottle for 3 hours at 50 C. and at room temperatureovernight. The reaction product is added to 50 ml. of 1:1 HCl and thevolume made up to 200 ml. with distilled water. The hydrochloride isfiltered and washed with 50 ml. of 1:4 HCl, and dried. The dryhydrochloride was then washed with a little ethyl acetate. The yield was9.1 grams of dodecyl Z-dimethylaminoethyl sulfoxide hydrochloride, M.P.162-4" C. Dodecyl Z-diethanolaminoethyl sulfoxide, C12H25SOCH2cHN(CHgCHzOH)2, dodecyl 2-morph0- linoethyl sulfoxide,

/CH2-CH2 CuHzaSOCHaCHzN /O CH2CH3 and dodecyl 2-piperidinoethyl CH2CH1/CH2 CHz-CH; were also prepared by this method, from diethanol amine,morpholine and piperidine, respectively.

The compounds found useful according to this inventron are listed belowtogether with their melting point and the melting point of sulfonesprepared therefrom.

C 12H25S O CHzCHzN Meltin M 112' No. Compound N arne Fonnnla Point,Plfllli i C. Sulfone,

l 1 Dodecyl Z-dimethylaminoethyl sulioxide 0 211 CHzCH2N(CH3)2 59 42 2-Dodecyl 2-diethanolaminoethyl sulfoxide C12H25SOCH2GH2N(CH2CH2OH)1 26 41C Hzo Hz 3 Dodecyl 2-morpholinoethyl sulfoxide (21211 58 0 0 H O HZN 6766 C H2C Hg C Hz-C H2 4 Dodecyl 2-piperidinoethyl sulfoxide 012112580CHzCHzN CH2 57 42 C H -C H Example 2 This example shows a representativeformulation of a heavy duty liquid detergent utilizing the sulfoxides ofthis invention. These materials are exceptionally useful in dishwashingand in heavy duty laundry detergents. The examples uses a combination oflauric isopropanol amide and dodecyl Z-aminoethyl sulfoxides of thepresent invention as the foam stabilizing additive. The resultingdetergent composition produces an exceptionally stable foam in aqueoussolution.

Ingredient: Percent Dodecyl benzene sulfonic acid (90% active) 7.0Sodium xylene sulfonate (37% active) 18.9 Sodium silicate (37.5% solids)7.0 Potassium hydroxide 2.4 Dodecyl 2-aminoethyl sulfoxide 3.5 Lauricisopropanol amide 1.7 Tetrapotassium pyrophosphate 19.1 Water andmiscellaneous ingredients 40.4

Dodecyl Z-dimethylaminoethyl sulfoxide, dodecyl 2-Cliethanolaminoethylsulfoxide, dodecyl 2-morphol-inoethyl sulfoxide, and dodecyl2-piperidinoethyl sulfoxide were used and each produced an exceptionallystable foam in aqueous solutions.

We claim:

1. A compound of the formula References Cited UNITED STATES PATENTS2,750,357 6/1956 Bredereck et a1 260247.1

ALEX MAZEL, Primary Examiner.

J. TOVAR, Assistant Examiner.

